Water-insoluble monoazo-dyestuffs



United States Patent 3,118,873 WATER-WSOLUBLE MON OAZO-DYESTUFFS HelmutGies, Hot'heim, Taunus, and Wilhelm Happe,

Schwalbaeh, Taunus, Germany, assignors to Farbwerke HoeclistAktiengesellschaft vormals- Meister Lucius & Briining, Frankfurt amMain, Germany, a

corporation of Germany No Drawing. Filed Apr. 24, 1961, Ser. No. 104,822

Claims priority, application Germany Apr. 28, 1960 6 Claims. (Cl.260205) The present invention relates to new water-insolublemonoazo-dyestuffs and to a process for their manufacture; moreparticularly it relates to new monoazo-dyestuffs corresponding to thefollowing general formula wherein Z represents a negative substituentwhich does not impart solubility in water and R stands for a hydrogenatom or an alkyl group of low molecular weight, and the benzene nucleiA, B and C may contain further substituents which do not impartsolubility in Water.

We have found that water-insoluble monoazo-dyestufis of the generalformula mentioned above are obtained by coupling the diazonium compoundof an amine of the benzene series which carries in 4-position a negativesubstituent which does not impart solubility in water and besides maycontain in the benzene nucleus further substituents which do not impartsolubility in water, with an amine in position 4 of the general formula\CH CH so 3 wherein R stands for a hydrogen atom or an alkyl group oflow molecular weight and the benzene nuclei A and B may containsubstituents which do not impart solubility in water.

As substituents which do not impart solubility in water the benzenenucleus A can contain, for example, halogen atoms, low molecular alkylgroups, low molecular alkoxy groups and/ or acylamino groups, thebenzene nucleus B can contain, for example, a halogen atom, an alkyl oralkoxy group of low molecular weight, and the benzene nucleus C maycarry halogen atoms, alkoxy groups of low molecular weight,trifiuoromethyl and/or nitro groups.

As amines which are the basis of the diazo components to be applied andcontain in position 4 a negative substituent which does not impartsolubility in water, there may be used those l-aminobenzene derivativeswhich conatin in position 4 for example a halogen atom, a nitro, nitrileor trifluoromethyl group and which, besides, may be substituted on thebenzene nucleus by further groups which do not impart solubility inwater such, for example, as halogen atoms, nitro and alkoxy groups.

The amines of the above-mentioned general Formula II which are used ascoupling components may be sub stituted at the benzene nucleus A bygroups which do not impart solubility in water such, for example, ashalogen atoms, alkyl, trifluoromethyl, alkoxy or acylamino groups, andon the benzene nucleus B by groups which do not 3,118,873 Patented Jan.21, 1964 impart solubility in water such, for example, as halogen atoms,alkyl, trifiuoromethyl or alkoxy groups.

The coupling is effected in an acid medium, if desired in the presenceof acid-binding agents such, for example, as sodium acetate, magnesiumoxide or pyridine. The new dyestuifs so obtained are suitably worked upin usual manner by kneading with known dispersing agents to obtain dyepreparations. The new dyestuifs yield on materials of polyester fibers,especially of polyethylene ter-. ephthalate fibers, valuable dyeingspossessing excellent properties of fastness, particularly a very goodfastness to sublimation. For coloring polyester materials the newdyestufls are suitably used in the form of the aforesaid dyepreparations which are applied in aqueous suspension at temperaturesabove C. under pressure or at about 100 C. with the addition of usualcarriers.

The new dyestuffs yield on materials of polyethylene terephthalatefibers yellow, orange, red, brown and blue tints.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto.

Example 1 196.5 grams of 2,4,6-trichloro-l-aminobenzene are diazotizedin the usual manner and the diazo solution so obtained is slowly addedto a solution of 303 grams of l-(N- l-'-methylphenylsulfonylethyl-Imethylamino) 3- methylbenzene in 1500 grams of hydrochloric acid of 36%strength. After one hour the reaction mixture is made up to 15 literswith water and after 24 hours the separated dyestutl is filtered oil anddried. It is an orange crystalline powder which dyes in dispersed form afabric of polyethylene terephthalate fibers in the pesence ofo-phenylphenol as carrier, at 100 C., deep golden yellow tints. Thedyeings obtained possess a very good fastness to light and sublimation.

Instead of the above-mentioned o-phenylphenol there may also be usedother carriers such, for example, as diphenyl, chlorobenzene and2-hydroxytoluene-3-carboxylic acid methyl ester.

Example 2 207 grams of 2,6-dichloro-4-nitro-l-aminobenzene arediazotized in the usual manner. The diazo solution so obtained is slowlyadded to a solution of 303 grams of1-(N-4-methylphenylsulfonylethyl-N-methylamino) 3- methylbenzene in 1500grams of sulfuric acid of 75% strength. After one hour the reactionmixture is made up to 15 liters with water and after 24 hours theseparated dyestuif is filtered oil and dried. It is a violet brownpowder which in dispersion dyes materials of polyethylene terephthalatefibers at C. copper brown tints. The dyeing so obtained possesses a verygood fastness to light and sublimation.

The following table contains a number of further water-insolublemonoazo-dyestuifs which may be obtained according to Examples 1 and 2.They correspond to the following formula and are distinguished in thefollowing table by the radicals R, R R X and Y as well as by their tinton materials of polyethylene terephthalate fibers.

'l'int on materials of Example R X Y R; R2 polyethylene tercphthalatefibers 2,6-diehloro-4-nitr0- brown.

Do. Do. orange. yellow.

D0. violet.

10 (0 OCI'IZ NHCOOH3"- II blue. 11 2,4-ilinitro-G-bro1no- OCHa NHCOOH IIDo.

pron 2-chloro-4-nitrophenyl H CH3 CH; scarlet 2,41linitro-G-1110Lhoxy- HCH3 CH3 claret.

phenyl. l-nitro-zimcthoxy- H H OH: phenyl scarlet leny. 211itrii-etntluoroineth- H CH3 CH3 4-cl1l0r0pl10nyl orange.

preny. 4-cyano-2,5-di1nethoxy- H CH3 CH; 4-methoxyphengolden yellow.

16H 2,4,Mrinitrophcnyl 00E; NHCOCH II 4-methylph0nyl. turquoise.2,6-diehloro-enitr0- H CH3 02115 0 brown.

phcnyl.

We claim: 4. The water-insoluble monoazo-dyestulf having the I o 1.Water insoluble monoazo-dyestulls having the formula formula R R R4 ClOOH;

l 1 /R1 1 I, I CHrCHz-SOrO-Ra CHz-CHz-SOrOCH; R3 B5 C1 CH3 wherein Zrepresents a member selected from the group consisting of a chlorineatom, nitro, cyano and trifluoromethyl groups, R represents a memberselected from the group consisting of a hydrogen atom, chlorine atom,bromine atom, methoxy, and nitro groups, R represents a member selectedfrom the group consisting of the chlorine atom, methoxy, and nitrogroups, R represents a member selected from the group consisting of ahydrogen atom and a methoxy group, R represents a member selected fromthe group consisting of a hydrogen atom, a chlorine atom, methyl, andacetylamino atom groups, R represents a member selected from the groupconsisting of a hydrogen atom and a lower alkyl group, R represents amember selected from the group consisting of a hydrogen atom, chlorineatom, methyl, and methoxy groups, and R represents a member selectedfrom the group consisting of a hydrogen atom and a methoxy group.

2. The Water-insoluble monoazo-dyestuff having the formula 3. Thewater-insoluble monoazo-dyestuff having the formula CNa formula 5. Thewater-insoluble monoazo-dyestuif having the References Cited in the fileof this patent UNITED STATES PATENTS Knight July 22, 1937 Knight Oct. 4,1938 McNally Apr. 17, 1945 Heywood June 28, 1949 Merian Apr. 8, 1958Dittmar et al Nov. 7, 1961

1. WATER INSOLUBLE MONOAZO-DYESTUFFS HAVING THE FORMULA